CN110252157A - A kind of reinforced metal composite ceramic film and preparation method thereof - Google Patents
A kind of reinforced metal composite ceramic film and preparation method thereof Download PDFInfo
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- CN110252157A CN110252157A CN201910616780.5A CN201910616780A CN110252157A CN 110252157 A CN110252157 A CN 110252157A CN 201910616780 A CN201910616780 A CN 201910616780A CN 110252157 A CN110252157 A CN 110252157A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2325/22—Thermal or heat-resistance properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
A kind of reinforced metal composite ceramic film and preparation method thereof, the ceramic membrane successively include basal layer, transition zone and accurate layer；Basal layer is by elemental metals or sintering alloy powder；Transition zone is elemental metals or alloy powder, with compound or powder sintered hybrid ceramic composite layer；Accurate layer includes the powder sintered ceramic foam filter layer of alkali metal oxide doped ceramics, through fuse salt ion exchange on the outside of accurate layer.The method are as follows: (1) in elemental metals or alloy powder, forming agent is added, mixes, is cast, sintering；(2) it by elemental metals or alloy powder, mixes, is cast with compound or hybrid ceramic powder, sintering；(3) by alkali metal oxide doped ceramics powder spray, sintering, ion exchange is washed, dry,.Ceramic membrane filter precision of the present invention is high, and flux is big, uniform pore diameter, and toughness is high, resistance to thermal shock, high mechanical strength, and surface stress is strengthened.The method of the present invention is simple, at low cost, is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of ceramic membranes and preparation method thereof, and in particular to a kind of reinforced metal composite ceramic film and its system
Preparation Method.
Background technique
Being separated by filtration requirement of the industry to filtering material is to improve filtering traffic as far as possible, while reducing filter sheet
The filtration resistance of body, to reduce production energy consumption.However, often there is such contradiction: the filter material of filter core for filter
Gap is big could to obtain high filtration flux, but the opposite reduction for resulting in filtering accuracy.And high-precision filter material is needed filter material
Filtering accuracy be promoted to sub-micron even nanoscale, filtration flux will certainly be reduced.
The prior art in order to obtain high-precision filter core be all made of be ceramic material sintering gained Nano grade precision
Ceramic element.But such filter core haves the characteristics that porous ceramics brittleness is big, resistance to heat shocks energy is poor, mechanical strength is low.Tradition
Ceramic element due to the filtering accuracy of superficial layer it is very high, easily by the colloidal solid in solution because bridging effect formation more cause
Close cake layer, the permanent cake layer of colloidal nature, will lead to the blowback cleaning failure in period, finally causes to filter once being formed
System can not normal filtration.
CN102659447A, CN105693276A disclose a kind of pure silicon carbide ceramics production method, this method production
Filter core belongs to traditional ceramic element production method, and there are still traditional ceramics filter core brittleness is big, thermal shock resistance, filter core is easy disconnected
The problem of splitting.
CN102500245A discloses a kind of preparation method of metal-base ceramic composite filter membrane, is by porous metal film in electricity
Solution liquid Anodic Oxidation obtains transition zone, and ceramic powders are then prepared into slurry and are coated on transition zone, composite filter element is obtained.It is real
On border, technology transition zone as obtained by oxidation and subsequent ceramic layer are all used as oxide skin(coating), and product is microcosmic after high temperature sintering
Interface belongs to metal and transits directly to ceramic coating, and the filter core of this spline structure is in varying temperature environment, due to metal and ceramic expansion
Coefficient is inconsistent, can directly result in the spalling failure of ceramic coating.And filter core product is one in itself during the sintering process from height
Temperature arrives the process of room temperature, which almost produce product qualified out in enormous quantities using this method.Therefore, this method
There is no thoroughly solve the spallation problems of metal layer and ceramic layer under temperature stress.
CN109364583A discloses a kind of Industrial cleaning facility Ti-Ti6Si4The preparation of outer wall light type metallic filtering film tubing
Method is to be sintered jointly with Titanium powder and silicon metal powder, obtains Titanium/Ti6Si4Cermet composite filter element.But
This method has what application range was limited: firstly, this method is only applicable to Titanium and Ti6Si4Metallic compound is answered
It closes, for the compound invalid of other metals and ceramic powders, especially when filtration system contains fluorine ion and strongly basic medium, this
Kind filter core is easy to that corrosion failure occurs；Secondly, producing the raw material metal titanium powder of the filter core and silicon metal powder is all difficult
Nano-precision raw material are obtained, when needing to prepare the filter core of nano-precision, this method is difficult to solve the problems, such as high-precision；
Again, this method prepares composite filter element using isostatic pressing process, the thickness of filter core especially secondary filter layer can not accomplish it is very thin,
Therefore, the filtration flux of product is smaller, while blowback effect is also poor.
To sum up, it would be highly desirable to find one kind overcome brittleness existing for traditional ceramics filter core is big, resistance to heat shocks can poor, mechanical strength
Low, the defects of blowback performance is poor cermet composite filter membrane technology.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of filtering essence
Degree is high, and filtration flux is big, and uniform pore diameter, thickness is thin, and toughness is high, good, the high mechanical strength of resistance to heat shocks energy, and easy blowback cleaning is thorough
Eliminate thermal stress damage, the reinforced metal composite ceramic film having a wide range of application in bottom.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of work
Skill is simple, at low cost, is suitable for the preparation method of the reinforced metal composite ceramic film of industrialized production.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of reinforced metal composite ceramic film, successively
Including basal layer, transition zone and accurate layer；The basal layer is formed by elemental metals or sintering alloy powder；The transition zone is
Elemental metals or alloy powder, with composite ceramics or hybrid ceramic it is powder sintered made of composite layer；The precision layer includes alkali
Ceramic foam filter layer made of the sintering of doped metallic oxide ceramic powders, and on the outside of accurate layer through alkali metal fusion salt and/
Or rare earth fuse salt ion exchange.Metallic substrate layer primarily serves the effect for improving filter membrane mechanical strength and toughness, prevents filter core
Fracture；Transition zone plays the combination stress between smooth metallic basal layer and ceramic layer, improves the thermal shock resistance of filter core；Essence
Close layer is ceramic layer, main to provide filter membrane high filtering accuracy, and filtering accuracy is equal to the filtering accuracy of ceramic filtration membrane.
Preferably, the alkali of the alkali metal element in the alkali metal oxide doped ceramics powder and alkali metal fusion salt gold
It is not exactly the same or entirely different to belong to element, and the diameter of the alkali metal element of alkali metal fusion salt >=alkali metal oxide doping
The diameter of alkali metal element in ceramic powders.It is formed with accurate layer by lithia doped ceramics is powder sintered, sodium hydroxide and hydrogen
The mixed melting salt of potassium oxide carries out for ion exchange: the oxidation lithium concentration of accurate layer is relatively high, the oxidation in fuse salt
Lithium concentration is zero, and the potassium ion and Na ion concentration in fuse salt are very high, under the driving of concentration difference effect, the lithium of accurate layer from
Son is spread to fuse salt, and the potassium ion and sodium ion in fuse salt are spread to accurate layer；By the time for controlling ion exchange
The lithium concentration of accurate layer can be made to gradually reduce from Inside To Outside, at the same potassium ion and sodium ion accurate layer concentration from
Outside gradually reduces inwardly；Since sodium ion and potassium ion are bigger than the radius of lithium ion, so that the surface of accurate layer is opposite
Compression, the stress changes original stress state of accurate layer, to effectively adjust and improve pottery are generated before processing
The binding force of ceramics and metal layer in porcelain film, to enhance the impact resistance of accurate layer in ceramic membrane.
Preferably, the content for the alkali metal element that the alkali metal oxide doped ceramics powder introduces is on the inside of accurate layer
It is gradually decreased on the outside of to accurate layer.
Preferably, in addition to alkali metal identical with alkali metal oxide, the alkali metal fusion salt and/or rare earth fuse salt
The alkali metal of introducing and/or the content of the rare earth element side outside accurate layer are gradually decreased to accurate layer inside.
Since the alkali metal of fuse salt and the alkali metal of accurate layer doping are not exactly the same or entirely different, thus in ion
In exchange process, due to concentration difference, the diffusion of ion concentration has occurred, forms ion concentration gradient, and then realize ceramic membrane table
The reinforcing of face stress.When one of alkali metal that alkali metal fusion salt introduces is identical as one of the alkali metal that alkali metal oxide introduces
When, the alkali metal concn trend that alkali metal oxide introduces be still out of accurate layer side melted to gradually decreasing on the outside of accurate layer
The addition for melting the identical alkali metal of this in salt is only intended to adjust the ratio of sodium in final accurate layer, potassium ion.
Preferably, the alkali metal fusion salt is one or more of lithium hydroxide, sodium hydroxide or potassium hydroxide etc..
Preferably, the rare earth fuse salt is one of nitric acid rare earth, oxide rare earth or chloride rare earth etc. or several
Kind.
It is highly preferred that the fuse salt is the mixed melting salt of the sodium hydroxide that mass ratio is 2~4:1 and potassium hydroxide,
Or mass ratio is the mixed melting salt of 10~200:20~60:1 sodium hydroxide, potassium hydroxide and rare earth fuse salt.
Preferably, the mass ratio of the basal layer, transition zone and accurate layer is that 40~90:30~80:0.2~20 are (more excellent
Select 40~90:30~80:0.5~5.0).If basal layer quality is excessive or blocked up, the resistance of membrane filtration will increase, if base
Bottom layer quality is too small or excessively thin, then will lead to filter film strength it is inadequate, be easy to happen fracture；If transition zone quality is excessive or mistake
Thickness, then the number of plies is excessive, increases production cost, if transition zone quality is too small or excessively thin, the number of plies is very few, it is difficult to effectively eliminate gold
Belong to the stress between layer and ceramic layer；If accurate layer quality is excessive or blocked up, the resistance of filter membrane is improved, if accurate layer quality mistake
Small or excessively thin, then sintering defect therein is difficult to completely eliminate.
Preferably, in the transition zone, elemental metals or alloy powder, the quality with composite ceramics or hybrid ceramic powder
Than for 95~5:5~95 (more preferable 60~90:40~10).Metal filtration film has the characteristics that intensity height, good toughness, but filter core mistake
Filter precision is not easy to improve；And although ceramic element brittleness is big, thermal shock resistance is low, but is easy to prepare nano-precision
Filter core.If the two is combined the advantages of can effectively playing the two, while avoiding the defect of the two.
Preferably, the thickness ratio of the basal layer, transition zone and accurate layer be 0.5~2.0:0.1~1.5:0.01~
0.10 (more preferable 0.8~1.8:0.3~1.3:0.02~0.08).
Preferably, the transition zone is made of 1~10 layer (more preferable 2~6 layers).It is difficult if the number of plies of transition zone is very few
Combine stress that can increase substantially production cost if the number of plies of transition zone is excessive to effectively eliminate.
Preferably, in each layer of the transition zone, elemental metals or alloy, with the mass ratio of composite ceramics or hybrid ceramic from
Basal layer is successively reduced to accurate layer.The design principle of transition zone of the present invention are as follows: prepared, and made close to Metal Substrate by multilayer
Tenor is as high as possible in the transition zone of bottom, while to the greatest extent may be used close to the transition zone ceramic content of accurate ceramic foam filter layer
Can be high, so that the metal component and ceramic composition of filter core are in two sides all distribution gradients, the ratio of content between metal and ceramics
Variation is smooth, and constituent is more close, and combination stress is lower, so that the knot of metallic substrate layer and high technology ceramics layer be effectively reduced
Combined stress.
Preferably, in the transition zone each layer with a thickness of 10~1500 μm (more preferable 100~1000 μm).If transition zone
It is blocked up, then production cost can be improved, if transition zone is excessively thin, is difficult to effectively eliminate the stress between metal layer and ceramic layer.
Preferably, in the accurate layer, the alkali metal oxide doped ceramics powder be alkali metal oxide with it is compound
Ceramics or hybrid ceramic powder quality ratio are the mixture of 1:1~100 (more preferable 1:2~50, further preferred 1:3~30).
If alkali metal oxide dosage is very few, ceramic membrane can reinforcing degree it is inadequate, if alkali metal oxide dosage is excessive, influence essence
The intensity of close layer.
Preferably, in the accurate layer, ceramic foam filter layer with a thickness of 1~100 μm.If accurate layer is blocked up, can
The resistance of filter membrane is improved, if accurate layer is excessively thin, sintering defect therein is difficult to completely eliminate.
Preferably, the mean pore size of the ceramic foam filter layer is 5~100nm.
Preferably, in the basal layer and transition zone, the elemental metals are fe, elemental nickel, elemental copper or simple substance
Titanium etc..
Preferably, in the basal layer and transition zone, the alloy is stainless steel, Hastelloy or Aludirome etc..
Preferably, in the basal layer, the average grain diameter of the elemental metals or alloy powder is 30~800 mesh.If base
Underlying metal partial size is too low, although sintered products gap is big, flux is high, and mechanical strength can be too low, if basal layer metal partial size
Excessive, although sintered products intensity is high, gap is small, and filtration flux is too low.
Preferably, in the transition zone, the average grain diameter of the elemental metals or alloy powder is 30~2000 mesh.Due to
Ceramic fusing point is higher than melting point metal, for the temperature that metal powder and ceramic powders are sintered together in matching transition layer, ceramics
Powder need to be thinner, and the particle of corresponding metal powder needs thicker.
Preferably, in the transition zone and accurate layer, the composite ceramics are oxide ceramics, nitride ceramics, carbonization
A kind of or classes of compound in object ceramics, boride ceramics, silicide ceramics or metal crystalline substance compound etc..It is highly preferred that
Compound oxidate ceramic is that alumina/silica composite ceramics, alumina-zirconia composite ceramics or zirconium oxide/yttrium oxide are multiple
Close ceramics etc..
Preferably, in the transition zone and accurate layer, the hybrid ceramic is oxide ceramics, nitride ceramics, carbonization
A kind of or classes of mixture in object ceramics, boride ceramics, silicide ceramics or metal crystalline substance compound etc..It is highly preferred that
Mixed oxide ceramics are aluminium nitride silicon nitride hybrid ceramic, zirconia alumina hybrid ceramic or silica zirconium oxide mixing pottery
Porcelain etc..
Preferably, in the transition zone and accurate layer, the average grain diameter of the composite ceramics or hybrid ceramic powder is 300
~10000 mesh.Ceramic foam filter layer need to have highest filtering accuracy, therefore the ceramic particle granularity selected is also relatively thin.
Preferably, in the accurate layer, the average grain diameter of the alkali metal oxide is 2000~10000 mesh.
Preferably, the accurate layer further includes the ceramic particle decorative layer on the outside of ceramic foam filter layer.Composite ceramic
There are certain sintering defects for ceramic foam filter layer made of porcelain or hybrid ceramic are powder sintered, by immersing hydrogels in ceramics
The ceramic particle decorative layer that layer surface is formed, since capillarity partial gel is by the local sintering crackle of ceramic foam filter layer
It absorbs, sintering defect disappears, and improves the filtering accuracy of filter membrane.
Preferably, the mass ratio of the ceramic particle decorative layer and ceramic foam filter layer is 0.04~0.45:1.Ceramics
The main function of particle modification layer be repair ceramic foam filter layer sintering defect produced during the preparation process, if quality it is excessive or
Thickness is blocked up, then can reduce filtration flux, if quality is too small or thickness is excessively thin, is difficult to play and eliminates ceramic layer sintering defect
Effect.
Preferably, the ceramic particle decorative layer is formed by 1~4 layer.
Preferably, in the ceramic particle decorative layer each layer with a thickness of 1~30 μm.
Preferably, ceramic particle decorative layer gel made of composite ceramics or hybrid ceramic powder is sintered.
Preferably, the average grain diameter of the composite ceramics or hybrid ceramic powder for gel to be made is 5~100nm.
Ceramic particle decorative layer has highest filtering accuracy, therefore the ceramic particle granularity selected is also relatively thin.
It is as follows that the present invention further solves technical solution used by its technical problem: a kind of reinforced metal composite ceramic film
Preparation method, comprising the following steps:
(1) in elemental metals or alloy powder, forming agent is added, after mixing, heating curtain coating, vacuum-sintering obtains substrate
Layer；
(2) by elemental metals or alloy powder, after mixing with composite ceramics or hybrid ceramic powder, heating is cast to step
(1) on gained basal layer, vacuum-sintering forms transition zone, obtains intermediate products；
(3) by alkali metal oxide doped ceramics powder spray on the transition zone of the intermediate products obtained by the step (2), vacuum
Sintering, forms ceramic foam filter layer, and outer by ceramic foam filter layer is placed on alkali metal fusion salt and/or rare earth fuse salt
Middle carry out ion exchange is washed, dry, obtains reinforced metal composite ceramic film.
Preferably, in step (1), the dosage of the forming agent be equivalent to elemental metals or alloy powder quality 0.1~
20.0% (more preferable 0.5~15.0%).If the dosage of forming agent is very few, it is difficult to normally apply casting technology, if molding
The dosage of agent is excessive, then will increase production cost, while causing product carbon content exceeded.Forming agent during the sintering process can be whole
Volatilization is decomposed, and forming agent is not contained in basal layer.
Preferably, in step (1), the forming agent be polyethylene glycol, polyolefin, paraffin, polyacrylamide, polyurethane or
One or more of methylcellulose etc..
Preferably, in step (1), the mixed temperature is room temperature~150 DEG C, and the time is 1~3h.If the mixed time
It is too short, then it is difficult to effectively be uniformly mixed, if mixed overlong time, wastes device resource and the energy.
Preferably, in step (1), the temperature of the heating curtain coating is 60~150 DEG C, and the speed of curtain coating is 0.5~30m/
Min (more preferable 1~15m/min).Batch is more advantageous to using the tape casting and prepares qualified basal layer blank, and prepare
Base layer thickness is uniform, industrialized production easy to accomplish.If casting temperature is excessively high or excessive velocities, the viscosity of slurry is low, stream
The thickness prolonged is not easy to control, if the temperature of curtain coating is too low or speed is excessively slow, casting apparatus discharging is uneven, and influences production effect
Rate.
Preferably, in step (1), the temperature of the vacuum-sintering is 1000~1500 DEG C (more preferable 1200~1400
DEG C), vacuum degree is 1 × 10-1~1 × 10-4Pa, time are 2~8h.It can occur between metallic particles during vacuum-sintering
Bonding, so that basal layer has corresponding mechanical strength.If the temperature of vacuum-sintering is too low or the time is too short, it is difficult to complete
The sintering of effect, if the temperature of vacuum-sintering is excessively high or overlong time, porous metallic layers can densify or even metallic substrates
Layer is completely in molten state, and final sintering obtains steel plate.
Preferably, in step (2), the temperature of the heating curtain coating is 60~150 DEG C (more preferable 80~120 DEG C), curtain coating
Speed be 0.5~30m/min (more preferable 1~15m/min).Batch is more advantageous to using the tape casting and prepares qualified transition
Layer, and the transition region thickness prepared is uniform, industrialized production easy to accomplish.If casting temperature is excessively high or excessive velocities, starch
The viscosity of material is low, and the thickness of curtain coating is not easy to control, if the temperature of curtain coating is too low or speed is excessively slow, casting apparatus discharging is uneven
It is even, and influence production efficiency.
Preferably, in step (2), the temperature of the vacuum-sintering is 1000~1500 DEG C, and vacuum degree is 1 × 10-1~1 ×
10-4Pa, time are 2~12h (more preferable 2~10h).Bonding between metallic particles, ceramics can occur during vacuum-sintering
Bonding, ceramic particle between particle and metal powder and the bonding between ceramic particle, so that transition zone has corresponding machine
Tool intensity.If the temperature of vacuum-sintering is too low or the time is too short, it is difficult to complete effectively to be sintered, if the temperature mistake of vacuum-sintering
High or overlong time, then metallic particles therein can densify.
Preferably, in step (2), operation >=1 time of powder mixing, heating curtain coating, vacuum-sintering is repeated, multilayer mistake is obtained
Cross layer.
Preferably, in step (3), the temperature of the vacuum-sintering is 1200~1600 DEG C (more preferable 1300~1500
DEG C), vacuum degree is 1 × 10-1~1 × 10-4Pa, time are 2~14h (more preferable 8~12h).It can occur during vacuum-sintering
Bonding between ceramic particle and ceramic particle, and form porous ceramic structure.If the temperature of vacuum-sintering is too low, ceramic layer
Be difficult to complete effectively to be sintered, if the temperature of vacuum-sintering is excessively high, the metal in basal layer and transition zone that has been formed at
Dividing may densify, or even fusing.
Preferably, in step (3), the alkali metal fusion salt and/or rare earth fuse salt and alkali metal oxide doping are made pottery
The mass ratio of porcelain powder is 1~100:1 (more preferable 5~50:1).If alkali metal oxide dosage is very few, ceramic membrane can be strengthened
Degree is inadequate, if alkali metal oxide dosage is excessive, influences the intensity of accurate layer.
Preferably, in step (3), the temperature of the ion exchange is 200~800 DEG C (more preferable 400~700 DEG C), when
Between be 0.5~8.0h (more preferable 1~5h).If the temperature of ion exchange is too low, ion exchange is difficult to realize, if ion exchange
Temperature it is excessively high, then fuse salt can corrode the metallic substrate layer of metal composite ceramal film；If the time mistake of ion exchange
Short, then ion exchange is insufficient, stress can reinforcing degree it is inadequate, if the overlong time of ion exchange, ion exchange are excessively filled
Divide even up to equilibrium state, the alkali metal ion even concentration that accurate layer exchanges everywhere, it is difficult to realize the gradient of exchange ion
Variation, it is stress reinforced to run counter to desire.
Preferably, in step (3), before ion exchange, in the outside of ceramic foam filter layer, impregnate composite ceramics or
Gel made of hybrid ceramic powder, vacuum-sintering form ceramic particle decorative layer.
Preferably, the temperature of the dipping is 50~80 DEG C, and the time is 0.5~15min (more preferable 6~12min).If leaching
The temperature of stain is too low or the time is too short, then the viscosity of gel is larger, is not easy homogeneous impregnation, if dipping temperature is excessively high or time mistake
Long, then gel is easy to happen dehydration loss of stability in air.
Preferably, the mass fraction of the gel is 1~50% (more preferable 5~30%).If the mass fraction mistake of gel
Low, then the dipping time needed increases, if the mass fraction of gel is excessively high, gel is unstable.
Preferably, the temperature of the vacuum-sintering is 1200~1600 DEG C, and vacuum degree is 1 × 10-1~1 × 10-4Pa, when
Between be 2~14h (more preferable 4~10h).During vacuum-sintering, since capillary theory is preferentially impregnated into ceramic layer defects
Gel and the gel that is deposited on ceramic foam filter layer the sintering between ceramic particle occurs.If the temperature mistake of vacuum-sintering
Low, then Ceramic gel is difficult to complete effectively to be sintered, if the temperature of vacuum-sintering is excessively high, the basal layer formed and transition
Metal component in layer may densify, or even fusing.
Preferably, repeated impregnations, vacuum-sintering operation >=1 time, obtain multi-layer ceramics particle modification layer.
Beneficial effects of the present invention are as follows:
(1) filtering accuracy of reinforced metal composite ceramic film of the present invention may be up to 1~50nm, filtration flux up to 500~
3000L/h；Uniform pore diameter has precision, uniform pore diameter index much higher than metal filtration film；
(2) reinforced metal composite ceramic film of the present invention can by change exchange ion type and ion exchange time,
Ceramic membrane surface reinforcing degree is controlled, to control the tensile stress of surface ceramic coat, unstressed or tensile stress state is come
Meets the needs of different stress field conjunction；
(3) reinforced metal composite ceramic film of the present invention has thickness thin, due in structure design there is metal, ceramics to coordinate
The characteristics of dividing consecutive variations, therefore have both metal phase, ceramic phase toughness height, good, the high mechanical strength of resistance to heat shocks energy, easy blowback cleaning
The advantages of, and in use, being effective against damage caused by temperature change under varying temperature environment；
(4) reinforced metal composite ceramic film of the present invention can be widely applied to industrial wastewater, high temperature corrosion gas cleaning etc.
Field can also apply to the various filtration systems with dramatic temperature variation；
(5) the method for the present invention simple process and low cost is suitable for industrialized production.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
The mass ratio of aluminium nitride and silicon nitride in aluminium nitride silicon nitride hybrid ceramic powder used in the embodiment of the present invention
For 72:27, the mass ratio of aluminium oxide and silica is 73:24, zirconia alumina in alumina/silica composite ceramic powder
The mass ratio of zirconium oxide and aluminium oxide is 10:90 in hybrid ceramic powder；Raw material used in the embodiment of the present invention or chemistry examination
Agent is obtained by routine business approach unless otherwise specified.
A kind of reinforced metal composite ceramic film embodiment 1
The reinforced metal composite ceramic film successively includes 90kg basal layer, 30kg transition zone and 0.55kg precision layer；
The basal layer is sintered by the simple substance titanium powder of 50 mesh of average grain diameter；The basal layer with a thickness of 1800 μ
m；
The transition zone is formed by 1 layer, is the simple substance titanium powder and the nitridation of 3000 mesh of average grain diameter of 800 mesh of average grain diameter
Aluminium silicon nitride hybrid ceramic powder is composite layer made of 70:30 sintering with mass ratio；The transition zone with a thickness of 750 μm；
The precision layer is 0.05kg, the nitrogen of lithia that average grain diameter is 2000 mesh and 0.5kg, 5000 mesh of average grain diameter
Change ceramic foam filter layer made of the sintering of aluminium silicon nitride hybrid ceramic mixture of powders, and be 3 through mass ratio on the outside of accurate layer:
The mixed melting salt ion exchange of 1 sodium hydroxide and potassium hydroxide；The content of elemental lithium out of accurate layer side to outside accurate layer
Side gradually decreases, potassium, sodium element content outside accurate layer side to gradually decreasing on the inside of accurate layer；The ceramic foam filter layer
With a thickness of 20 μm；The mean pore size of the ceramic foam filter layer is 50nm.
A kind of reinforced metal composite ceramic film embodiment 2
The reinforced metal composite ceramic film successively includes 50kg basal layer, 45kg transition zone and 2.11kg precision layer；
The basal layer powder sintered is formed by the stainless steel 310S of 400 mesh of average grain diameter；The basal layer with a thickness of
1200μm；
The transition zone is formed by 3 layers, from basal layer to accurate layer, the 1st layer be 500 mesh of average grain diameter stainless steel 310S
The alumina/silica composite ceramic powder of powder and 5000 mesh of average grain diameter is compound made of being sintered with mass ratio for 90:10
Layer, the 2nd layer is the stainless steel 310S powder of 750 mesh of average grain diameter and the alumina/silica composite ceramic of 5000 mesh of average grain diameter
Porcelain powder is composite layer made of 50:50 sintering with mass ratio, the 3rd layer of stainless steel 310S powder for 800 mesh of average grain diameter with
The alumina/silica composite ceramic powder of 8000 mesh of average grain diameter is composite layer made of 10:90 sintering with mass ratio；It is described
Each layer of transition zone with a thickness of 350 μm；
The precision layer includes 0.1kg, the lithia that average grain diameter is 2000 mesh, and 0.01kg, average grain diameter are 3000 mesh
Alumina/silica composite ceramic powder mixture sintering of the sodium oxide molybdena with 10000 mesh of 1.9kg average grain diameter made of it is porous
Ceramic filter layer and 0.1kg are set on the outside of ceramic foam filter layer, by the alumina/silica composite ceramic of average grain diameter 100nm
Ceramic particle decorative layer made of the sintering of gel made of porcelain powder；And the hydrogen-oxygen that accurate layer outside is 150:50:1 through mass ratio
Change the mixed melting salt ion exchange of sodium, potassium hydroxide and lanthanum nitrate；Lithium, sodium element content out of accurate layer side to accurate layer
Outside gradually decreases, potassium, lanthanum element content outside accurate layer side to gradually decreasing on the inside of accurate layer；The ceramic foam filter
Layer with a thickness of 45 μm；The mean pore size of the ceramic foam filter layer is 10nm；The ceramic particle decorative layer is by 1 layer
Composition, with a thickness of 25 μm.
A kind of reinforced metal composite ceramic film embodiment 3
The reinforced metal composite ceramic film successively includes 40kg basal layer, 60kg transition zone and 0.65kg precision layer；
The basal layer powder sintered is formed by the Hastelloy of 300 mesh of average grain diameter；The basal layer with a thickness of
1100μm；
The transition zone is formed by 2 layers, from basal layer to accurate layer, the 1st layer be 200 mesh of average grain diameter Hastelloy powder
Composite layer made of the zirconia alumina hybrid ceramic powder of end and 3000 mesh of average grain diameter is sintered with mass ratio for 70:30,
2nd layer is the Hastelloy powder of 800 mesh of average grain diameter and the zirconia alumina hybrid ceramic powder of 3000 mesh of average grain diameter
It is composite layer made of 20:80 sintering with mass ratio；Each layer of transition zone with a thickness of 650 μm；
The precision layer includes 0.15kg, 10000 mesh of lithia and 0.45kg average grain diameter that average grain diameter is 4000 mesh
The sintering of zirconia alumina hybrid ceramic mixture of powders made of ceramic foam filter layer and 0.05kg be set to porous ceramics
On the outside of filter layer, ceramics made of the sintering of the gel made of the zirconia alumina hybrid ceramic powder of average grain diameter 20nm
Grain decorative layer；And the mixed melting salt through sodium hydroxide, potassium hydroxide and lanthanum chloride that mass ratio is 20:30:1 on the outside of accurate layer
Ion exchange；The content of elemental lithium out of accurate layer side to gradually decreasing on the outside of accurate layer, sodium, potassium, lanthanum element content from essence
It is gradually decreased on the inside of lateral accurate layer outside close layer；The ceramic foam filter layer with a thickness of 30 μm；The ceramic foam filter
The mean pore size of layer is 5nm；The ceramic particle decorative layer is formed by 2 layers, and thickness is followed successively by 5 μm, 3 μm from inside to outside.
A kind of preparation method embodiment 1 of reinforced metal composite ceramic film
(1) in 90kg simple substance titanium powder, 0.45kg methylcellulose is added, after mixing 3h under room temperature, at 90 DEG C, 4m/
Under min, heating curtain coating, at 1300 DEG C, 3 × 10-3Under Pa, vacuum-sintering 6h obtains basal layer；
(2) after 21kg simple substance titanium powder being mixed with 9kg aluminium nitride silicon nitride hybrid ceramic powder, at 90 DEG C, 4m/min
Under, heating is cast on basal layer obtained by step (1), at 1400 DEG C, 3 × 10-3Under Pa, vacuum-sintering 10h forms transition zone,
Obtain intermediate products；
(3) 0.05kg lithia and 0.5kg aluminium nitride silicon nitride hybrid ceramic mixture of powders are sprayed at step (2) institute
On the transition zone for obtaining intermediate products, at 1400 DEG C, 5 × 10-3Under Pa, vacuum-sintering 8h forms ceramic foam filter layer, will be porous
In the outer mixed melting salt for being placed on 3kg sodium hydroxide and 1kg potassium hydroxide of ceramic filter layer, at 550 DEG C, ion is carried out
2h is exchanged, is washed, it is dry, obtain reinforced metal composite ceramic film 1.
Through detecting, the filtering accuracy of reinforced metal composite ceramic film 1 obtained by the embodiment of the present invention is 50nm, and filtration flux is
2000L/h；Uniform pore diameter has precision, uniform pore diameter index much higher than metal filtering core；And toughness is high, high mechanical strength,
Easy blowback cleaning.
A kind of preparation method embodiment 2 of reinforced metal composite ceramic film
(1) in 50kg stainless steel 310S powder, 7.5kg polypropylene/paraffin (mass ratio 1:1) is added, at 150 DEG C
Under, after mixing 2h, at 130 DEG C, under 5m/min, heating curtain coating, at 1320 DEG C, 5 × 10-2Under Pa, vacuum-sintering 3h obtains substrate
Layer；
(2) after mixing 13.5kg stainless steel 310S powder with 1.5kg alumina/silica composite ceramic powder, 120
DEG C, under 5m/min, heating is cast on basal layer obtained by step (1), at 1450 DEG C, 5 × 10-2Under Pa, vacuum-sintering 4h is formed
1st layer of transition zone；
After 7.5kg stainless steel 310S powder is mixed with 7.5kg alumina/silica composite ceramic powder, at 120 DEG C,
Under 5m/min, heating is cast on the 1st layer of transition zone, at 1450 DEG C, 5 × 10-2Under Pa, vacuum-sintering 5h forms the 2nd layer of transition
Layer；
After 1.5kg stainless steel 310S powder is mixed with 13.5kg alumina/silica composite ceramic powder, at 120 DEG C,
Under 5m/min, heating is cast on the 2nd layer of transition zone, at 1450 DEG C, 5 × 10-2Under Pa, vacuum-sintering 6h forms the 3rd layer of transition
Layer, obtains intermediate products；
(3) 0.1kg lithia, 0.01kg sodium oxide molybdena and 1.9kg alumina/silica composite ceramic powder mixture are sprayed
It is applied on the transition zone of intermediate products obtained by step (2), at 1500 DEG C, 5 × 10-2Under Pa, vacuum-sintering 10h forms porous pottery
Porcelain filter layer；
In the outside of ceramic foam filter layer, at 80 DEG C, matter made of oxide impregnation aluminium/silica composite ceramic powder
The gel 6min for measuring score 30%, at 1500 DEG C, 5 × 10-2Under Pa, vacuum-sintering 4h forms ceramic particle decorative layer；
By the outer mixing for being placed on 15kg sodium hydroxide, 5kg potassium hydroxide and 0.1kg lanthanum nitrate of ceramic particle decorative layer
In fuse salt, at 550 DEG C, ion exchange 2h is carried out, is washed, it is dry, obtain reinforced metal composite ceramic film 2.
Through detecting, the filtering accuracy of reinforced metal composite ceramic film 2 obtained by the embodiment of the present invention is 10nm, and filtration flux is
800L/h；Uniform pore diameter has precision, uniform pore diameter index much higher than metal filtering core；And toughness is high, high mechanical strength,
Easy blowback cleaning.
A kind of preparation method embodiment 3 of reinforced metal composite ceramic film
(1) in 40kg Hastelloy powder, 0.3kg polyacrylamide is added, after mixing 1h under room temperature, at 80 DEG C, 8m/
Under min, heating curtain coating, at 1400 DEG C, 1 × 10-2Under Pa, vacuum-sintering 2h obtains basal layer；
(2) after 21kg Hastelloy powder being mixed with 9kg zirconia alumina hybrid ceramic powder, at 80 DEG C, 8m/
Under min, heating is cast on basal layer obtained by step (1), at 1100 DEG C, 4 × 10-2Under Pa, vacuum-sintering 4h forms the 1st layer
Transition zone；
After 6kg Hastelloy powder is mixed with 24kg zirconia alumina hybrid ceramic powder, at 80 DEG C, 8m/min
Under, heating is cast on the 1st layer of transition zone, at 1300 DEG C, 4 × 10-2Under Pa, vacuum-sintering 8h forms the 2nd layer of transition zone, obtains
Intermediate products；
(3) 0.15kg lithia and 0.45kg zirconia alumina hybrid ceramic mixture of powders are sprayed at step (2)
On the transition zone of gained intermediate products, at 1300 DEG C, 4 × 10-2Under Pa, vacuum-sintering 12h forms ceramic foam filter layer；
In the outside of ceramic foam filter layer, at 60 DEG C, matter made of oxide impregnation zirconium aluminium oxide hybrid ceramic powder
The gel 12min for measuring score 10%, at 1500 DEG C, 6 × 10-2Under Pa, vacuum-sintering 8h forms the 1st layer of ceramic particle decorative layer；
In the outside of the 1st layer of ceramic particle decorative layer, at 60 DEG C, oxide impregnation zirconium aluminium oxide hybrid ceramic powder is made
Mass fraction 6% gel 10min, at 1400 DEG C, 6 × 10-2Under Pa, vacuum-sintering 5h forms the 2nd layer of ceramic particle modification
Layer；
Outer by ceramic particle decorative layer is placed on the mixed of 10kg sodium hydroxide, 15kg potassium hydroxide and 0.5kg lanthanum chloride
It closes in fuse salt, at 600 DEG C, carries out ion exchange 3.5h, wash, it is dry, obtain reinforced metal composite ceramic film 3.
Through detecting, the filtering accuracy of reinforced metal composite ceramic film 3 obtained by the embodiment of the present invention is 5nm, and filtration flux is
1500L/h；Uniform pore diameter has precision, uniform pore diameter index much higher than metal filtering core；And toughness is high, high mechanical strength,
Easy blowback cleaning.
Comparative example 1
(1) in 40kg Hastelloy powder, 0.3kg polyacrylamide is added, after mixing 1h under room temperature, at 80 DEG C, 8m/
Under min, heating curtain coating, at 1400 DEG C, 1 × 10-2Under Pa, vacuum-sintering 2h obtains basal layer；
(2) after 21kg Hastelloy powder being mixed with 9kg zirconia alumina hybrid ceramic powder, at 80 DEG C, 8m/
Under min, heating is cast on basal layer obtained by step (1), at 1100 DEG C, 4 × 10-2Under Pa, vacuum-sintering 4h forms the 1st layer
Transition zone；
After 6kg Hastelloy powder is mixed with 24kg zirconia alumina hybrid ceramic powder, at 80 DEG C, 8m/min
Under, heating is cast on the 1st layer of transition zone, at 1300 DEG C, 4 × 10-2Under Pa, vacuum-sintering 8h forms the 2nd layer of transition zone, obtains
Intermediate products；
(3) by the transition zone of 0.6kg zirconia alumina hybrid ceramic powder spray intermediate products obtained by step (2)
On, at 1300 DEG C, 4 × 10-2Under Pa, vacuum-sintering 12h forms ceramic foam filter layer；
In the outside of ceramic foam filter layer, at 60 DEG C, matter made of oxide impregnation zirconium aluminium oxide hybrid ceramic powder
The gel 12min for measuring score 10%, at 1500 DEG C, 6 × 10-2Under Pa, vacuum-sintering 8h forms the 1st layer of ceramic particle decorative layer；
In the outside of the 1st layer of ceramic particle decorative layer, at 60 DEG C, oxide impregnation zirconium aluminium oxide hybrid ceramic powder is made
Mass fraction 6% gel 10min, at 1400 DEG C, 6 × 10-2Under Pa, vacuum-sintering 5h forms the 2nd layer of ceramic particle modification
Layer, obtains metal composite ceramal film 1.
The metal composite that reinforced metal composite ceramic film 1~3 of the present invention, commercially available ceramic membrane and comparative example 1 are not strengthened is made pottery
Porcelain film 1 carries out shock resistance comparative experiments according to GB4742-B4, and each filter membrane sample number is 5, tests different samples respectively
Notched bar impact strength, the results are shown in Table 1.
The reinforced metal composite ceramic film 1~3 of the present invention of table 1 and the impact of commercially available ceramic membrane and metal composite ceramal film 1 are tough
Property contrast table
As shown in Table 1, reinforced metal composite ceramic film 1~3 of the present invention is in impact flexibility test respectively than commercially available ceramics
Filter core improves about 40~140%, 140~270%, 200~370%；Reinforced metal composite ceramic film 3 of the present invention is not compared to having
The 1 metal composite ceramal film 1 of comparative example of ion-exchange treatment is carried out, impact flexibility improves about 100~210%, illustrates the present invention
After strengthening, impact flexibility increases substantially reinforced metal composite ceramic film 1~3.
Claims (10)
1. a kind of reinforced metal composite ceramic film, it is characterised in that: successively include basal layer, transition zone and accurate layer；The base
Bottom is formed by elemental metals or sintering alloy powder；The transition zone be elemental metals or alloy powder, with composite ceramics or
Composite layer made of hybrid ceramic is powder sintered；The precision layer includes made of alkali metal oxide doped ceramics is powder sintered
Ceramic foam filter layer, and through alkali metal fusion salt and/or rare earth fuse salt ion exchange on the outside of accurate layer.
2. reinforced metal composite ceramic film according to claim 1, it is characterised in that: the alkali metal oxide doped ceramics
The alkali metal element of alkali metal element and alkali metal fusion salt in powder is not exactly the same or entirely different, and alkali metal fusion
The diameter of alkali metal element in the diameter of the alkali metal element of salt >=alkali metal oxide doped ceramics powder；The alkali metal oxygen
The content for the alkali metal element that compound doped ceramics powder introduces side out of accurate layer is gradually decreased to accurate layer outside；It removes and alkali
Outside the identical alkali metal of metal oxide, alkali metal and/or rare earth that the alkali metal fusion salt and/or rare earth fuse salt introduce
The content of element side outside accurate layer is gradually decreased to accurate layer inside；The alkali metal fusion salt is lithium hydroxide, hydroxide
One or more of sodium or potassium hydroxide；The rare earth fuse salt is in nitric acid rare earth, oxide rare earth or chloride rare earth
One or more；The fuse salt is the mixed melting salt or matter of the sodium hydroxide that mass ratio is 2~4:1 and potassium hydroxide
Amount is than the mixed melting salt for 10~200:20~60:1 sodium hydroxide, potassium hydroxide and rare earth fuse salt.
3. reinforced metal composite ceramic film according to claim 1 or claim 2, it is characterised in that: the basal layer, transition zone and essence
The mass ratio of close layer is 40~90:30~80:0.2~20；In the transition zone, elemental metals or alloy powder, with composite ceramic
The mass ratio of porcelain or hybrid ceramic powder is 95~5:5~95；The thickness ratio of the basal layer, transition zone and accurate layer is 0.5
~2.0:0.1~1.5:0.01~0.10；The transition zone is formed by 1~10 layer；In each layer of transition zone, elemental metals or
Alloy is successively reduced with the mass ratio of composite ceramics or hybrid ceramic from basal layer to accurate layer；Each layer in the transition zone
With a thickness of 10~1500 μm；In the precision layer, the alkali metal oxide doped ceramics powder is for alkali metal oxide and again
Ceramics or hybrid ceramic powder quality are closed than the mixture for 1:1~100；In the precision layer, the thickness of ceramic foam filter layer
Degree is 1~100 μm；The mean pore size of the ceramic foam filter layer is 5~100nm.
4. reinforced metal composite ceramic film described according to claim 1~one of 3, it is characterised in that: the basal layer and transition
In layer, the elemental metals are fe, elemental nickel, elemental copper or simple substance titanium；The alloy is stainless steel, Hastelloy or iron
Cr-Al alloy；In the basal layer, the average grain diameter of the elemental metals or alloy powder is 30~800 mesh；The transition zone
In, the average grain diameter of the elemental metals or alloy powder is 30~2000 mesh；It is described compound in the transition zone and accurate layer
Ceramics are in oxide ceramics, nitride ceramics, carbide ceramics, boride ceramics, silicide ceramics or metal crystalline substance compound
A kind of or classes of compound；In the transition zone and accurate layer, the hybrid ceramic is oxide ceramics, nitride pottery
A kind of or classes of mixture in porcelain, carbide ceramics, boride ceramics, silicide ceramics or metal crystalline substance compound；It is described
In transition zone and accurate layer, the average grain diameter of the composite ceramics or hybrid ceramic powder is 300~10000 mesh；The precision
In layer, the average grain diameter of the alkali metal oxide is 2000~10000 mesh.
5. reinforced metal composite ceramic film described according to claim 1~one of 4, it is characterised in that: it is described precision layer further include
Ceramic particle decorative layer on the outside of ceramic foam filter layer；The matter of the ceramic particle decorative layer and ceramic foam filter layer
Amount is than being 0.04~0.45:1；The ceramic particle decorative layer is formed by 1~4 layer；Each layer in the ceramic particle decorative layer
With a thickness of 1~30 μm；Ceramic particle decorative layer gel made of composite ceramics or hybrid ceramic powder is sintered；Institute
The average grain diameter for stating the composite ceramics or hybrid ceramic powder for gel to be made is 5~100nm.
6. a kind of preparation method of the reinforced metal composite ceramic film as described in one of Claims 1 to 5, which is characterized in that including
Following steps:
(1) in elemental metals or alloy powder, forming agent is added, after mixing, heating curtain coating, vacuum-sintering obtains basal layer；
(2) by elemental metals or alloy powder, after mixing with composite ceramics or hybrid ceramic powder, heating is cast to step (1)
On gained basal layer, vacuum-sintering forms transition zone, obtains intermediate products；
(3) by the transition zone of alkali metal oxide doped ceramics powder spray intermediate products obtained by step (2), vacuum is burnt
Knot, forms ceramic foam filter layer, and outer by ceramic foam filter layer is placed in alkali metal fusion salt and/or rare earth fuse salt
Ion exchange is carried out, is washed, it is dry, obtain reinforced metal composite ceramic film.
7. the preparation method of reinforced metal composite ceramic film according to claim 6, it is characterised in that: described in step (1)
The dosage of forming agent is equivalent to the 0.1~20.0% of elemental metals or alloy powder quality；The forming agent is polyethylene glycol, gathers
One or more of alkene, paraffin, polyacrylamide, polyurethane or methylcellulose；The mixed temperature be room temperature~
150 DEG C, the time is 1~3h；The temperature of the heating curtain coating is 60~150 DEG C, and the speed of curtain coating is 0.5~30m/min；It is described
The temperature of vacuum-sintering is 1000~1500 DEG C, and vacuum degree is 1 × 10-1~1 × 10-4Pa, time are 2~8h.
8. the preparation method of reinforced metal composite ceramic film described according to claim 6 or 7, it is characterised in that: in step (2),
The temperature of the heating curtain coating is 60~150 DEG C, and the speed of curtain coating is 0.5~30m/min；The temperature of the vacuum-sintering is
1000~1500 DEG C, vacuum degree is 1 × 10-1~1 × 10-4Pa, time are 2~12h；Repeat powder mixing, heating is cast, true
Operation >=1 time of sky sintering, obtains multilayer transition layer.
9. the preparation method of reinforced metal composite ceramic film according to one of claim 6~8, it is characterised in that: step (3)
In, the temperature of the vacuum-sintering is 1200~1600 DEG C, and vacuum degree is 1 × 10-1~1 × 10-4Pa, time are 2~14h；Institute
The mass ratio for stating alkali metal fusion salt and/or rare earth fuse salt and alkali metal oxide doped ceramics powder is 1~100:1；Institute
The temperature for stating ion exchange is 200~800 DEG C, and the time is 0.5~8.0h.
10. the preparation method of reinforced metal composite ceramic film according to one of claim 6~9, it is characterised in that: step
(3) it in, before ion exchange, in the outside of ceramic foam filter layer, impregnates made of composite ceramics or hybrid ceramic powder
Gel, vacuum-sintering form ceramic particle decorative layer；The temperature of the dipping is 50~80 DEG C, and the time is 0.5~15min；Institute
The mass fraction for stating gel is 1~50%；The temperature of the vacuum-sintering is 1200~1600 DEG C, and vacuum degree is 1 × 10-1~1
×10-4Pa, time are 2~14h；Repeated impregnations, vacuum-sintering operation >=1 time, obtain multi-layer ceramics particle modification layer.
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